Dialkyl s(1, 3, 3-trialkoxypropyl) phosphorothiolothionates



U s-m Pa en 2,908,707 DIALKYL S(1,3,3-TR,IALK0XYPR0PYL) PHQSPHOROTHTOLOTHTONATES Marvin A. McCall and Harry W. Coover, Jr., Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. "Application December 5, 1957 Serial No. 700,763 1 6 Claims. (01. 260-1461 y they have been employed as insecticides, fungicides, pes- I ticides and in'related uses. Consequently, it is of considerable importance to discover new and useful organophosphorus compounds and to have process for the production of such organophosphorus compounds. Therefore, it is an object of this invention to provide new and useful organophosphorus compounds. ject ofthis invention to provide a novel methodfor preparing the new and useful organophosphorus compounds. It is still another object of this invention to provide new and valuable insecticides that can be used in various insecticidal compositions. a

I In accordance with this invention it has been found that new organophosphorus compounds, useful as insecticides, can be prepared by reacting certain phosphorothiolothiomates withtrialkoxypropeneS. The newprod ucts of this invention have the structural formulai wherein R and R are selected from thegroup consisting of lower alkyl radicals containing 1 to 4 carbon atoms, haloalkyl (chloroethyl, chloropropyl, trichlorw ethyl, and thelike) radicals'containingl to 4 carbon atoms, alkoxyalkyl (methoxymethyl, methoxyethyl, methoxypropyl, and the like) radicals wherein the alkoxy and alkyl groups contain 1 to 4 carbonatoms, and R I R, and R are allsyl groups containing 1 to 2 carbon atoms. When the number of carbon atoms in R R and R is more than 3, the insecticidal activity of prodnet is decreased.

The compounds of this invention are prepared by reacting a" phosphorothiolothionate having the structural formula: \i i P-sH, V

wherein R R and R are as defined above.

In the practice of this invention we prefer to add one It is another obour invention c an be prepared bytheknown reaction of 4 moles of an aliphatic alcoholwithone mole of phos 2,908,707 Patented oct. s, less 2 of the reactants gradually to a reactor containing the other reactant. For example, the trialkoxypropene can beadded gradually to a reactor containing the phosphorothiolothionate reactant. verse procedure of addition of reactants canbe used and the phosphorothiolothionate reactants can be added to a reactor containing the trialkoxypropene. Normally it is desirable to employ a reactorprovided with adequate means' of agitation and," since the reaction is quite'ex othermic, it is also desirable to employ a reactor that is provided with adequate cooling means.

The operable temperature range for the reaction is generally from -25 to 150 C. and the preferred temperature range is from 25 to C. However, it will be realized that in some instances temperatures outside this range can be employed. The reaction t me usually varies from 0.5 to 8 hours, but longer and shorter reac; tion periods are sometimes used. Normally it is im-.

necessary to employa catalyst for the reactionv since thephosphorothiolothionate will react with the 'trialkoxypropene in the absence of a catalyst.

drocarbons aswell as the common ether and ester solvents. It is preferable to carry out the reaction using equimolar quantities of the reactants, but the ratio of reactants is subject to wide variation.

The phosphorothiolothionate reactants that are used in phorus pentasulfide." The trialkoxypropenes can be prepared by the pyrolysis of the 1,1,3,3-tetroalkoxypropanes which in turn can be prepared from malonaldehyde and the. appropriate alcohol. Trimethoxypropene is available commercially. i

The following examples are illustrative ofthe com-.

pounds within the scope of this invention, their method of preparation and their utility as insecticides.

, EXAMPLE 1 I a 0,0-diefliyl S-(1,3,3-trimethoxypropyl) phosphorothiolothiontlte '0,0 -die'thyl phosphorothiolothionate (0.1 mole) was. added dropwise'to 1,3,3-trimethoxypropenc (0.1 mole), with stirring. The reaction was exothermic and the temperature rose to about 45 C. After the addition was complete and the temperature had dropped to room temperature, the reaction was heated on a steam bath for 15 minutes. The product was an oil, n 1.4845.

EXAMPLE 2 0,0-dirnethyl S-(1,3, 3-trimeth0xypropyl) phosphorothiolothionate 0,0-dimethyl phosphorothiolothionate (0.1 mole) was reacted with 1,3,3-trimethoxypropene (0.1 mole)in the was an amber colored oil, n 1.4890.

Alternatively however, the re- If it is considered 1 desirable to employ a catalyst, there are certain catalysts that can be used. For example, the tertiary amines, 1

3 EXAMPLE 3 0,0-bis(2,2,Z-trichlorethyl) S-(1,3,3-trimethoxypropyl) phosphorothiolothionate CH3OOH-CH2CH(OCH3)2 v sixsxoom-ocn):

0,0-bis(2,2,2-trichloroethyl) phosphorothiolothionate (0.1 mole) Was reacted with 1,3,3'-trimethoxypropene (0.1;mole) in the same manner as described in Example 1. The product was a dark brown oil, n 1.5175.

EXAMPLE 4 O-ethyl; O-methyl S-(l,3,3-trimethoxypropyl) phosphorothiolothionate P(S)S-CHOH2CH(0CH3)9' C1130 OCH:

O-ethyl, O-methyl phosphorothiolothionate (0.1 mole) was added to 1,3,3-trimethoxypropene (0.1 mole) dissolved in 25 cc. of dry benzene containing 4 drops of triethyl' amine as catalyst. After the addition was completed the mixture was heated on a steam bath for 15 minutes: The reaction mixture was then vacuum stripped to remove the benzene solvent and any other volatile impurities. The product remaining was a dark oil, n 1;4860.

EXAMPLE 5 OQO-bisQ-chloroethyl) S-(1,3,3-triethoxypropyl) phosphorothialathionate (GlCHr-CH;0);P(S)SCHOH;CH(OCH O, O-bis(2-chloroethyl) phosphorothiolothionate (0.1 mole) was reacted with 1,3,3-triethoxypropene (0.1 mole) under the same reaction conditions as described in Example 1. The product was a brown oil.

EXAMPLE 6 0,0-bis(2 -methoxye thyl) S-(1,3,3-triethoxypropyl) phosphorothiolothionate (CH;OCzH O)zP(S)S-CH-CHz -CH(OCzH5)z 0,0-bis(2-methoxyethyl) phosphorothiolothionate (0.1 mole) was reacted with 1,3,3-triethoxypropene (0.1 mole) in the same manner as described in Examplel. The product was an amber colored oil.

EXAMPLE 7 0,0-diethyl S-(1-methoxy- 3,3 diethoxypropyl) phosphorothiolothionate This compound was prepared from 0.1 mole of 0,0- diethyl phosphorothiolothionate. and 0.1 mole of l-methoxy-3,3-ethoxy propene in the same manner as described in Example 1. The 1-methoxy-3,3-diethoxy propene was prepared by the same general method as is used for preparing the trimethoxy or triethoxypropenes except that the starting material was a mixed ethylmethyl acetal of malonaldehyde.

EXAMPLE 8 Use of compounds as insecticides.--Tests against mites were carried out in the following manner. Acetone solutions containing 1% of the candidate compounds were prepared and diluted with water to give solutions of the desired concentration for testing. Two heavily infested bean leaves containing adult two-spotted mites (Tetranychus bimaculatus Harvey) were carefully dipped inthe above solutions and dried in a gentle'air steam. The leaves were then placed on damppaper toweling in Petri dishes and observed after 24 hours for mortality among the adult mites. The percentage of the insects killed by different concentrations (parts per million) of toxicant can then be calculated; however, for comparison purposes it is more convenient to calculate the concentration of toxicant needed to kill of the test insects. This concentration in parts per million is known as the minimum lethal dose required to kill 85% of the test insects and is abbreviated LD 85. The toxicity data for the compounds of this invention are given below in Table 1. The toxicity data for several simple ether or acetal derivatives are given in Table II. By comparison it can be seen that 1,3,3-trialkoxypropyl phosphorothiolothionates are some 4-10 times as active as the type disclosed in the prior art and therefore the compounds of this invention are not only different structurally but also unexpectedly several times more active. It should be noted that tests using acetone-water solutions (contain ing none of the toxicant) kill none of the mites.

TABLE I LD 85 in Toxicant p.p.m. for

mites 1. O, O-Diethyl S-(l, 3, 3-trimcthoxypropyl) phosphoro- 9.

thiolothionateflflx. 1)

2. 0, O-Dimethyl S-(l, 3,

thiolothionate (Ex. 2).

3. O-Ethyl, O-methyl S-(l, 3, 3-trimethoxypropyl) phosphorothiolothionate (Ex. 4).

il-trimethoxypropyl) phosphoro- 9.

In like manner the other compounds of Examples 3, 5, 6, and 7 were found to have a very high order of miticidal activity. These compounds are also active aphicides, for example the product from Example 1 had an LD 85 of 20 p.p.m. for aphids.

TABLE II Toxicants of the Aeetal Type LD 85 in p.p.m.

for mites 1. O, O-Diethyl S-[l-(diethoxymethyl) ethyl] phosphorothiolothionate.

OHg-OH-OH (0 0111 2. O, O-Diethyl S-[l-(diethoxymethyl) propyl] phosphorothiolothionate.

Toxicants of the Ether Type 1. 0, O-Diethyl S-(l-ethoxy-Z-methyl) propyl phosphorothiolothionate (distilled analytical sample).

(CHOICE-0H4) 02H5 2. 0, O-Diethyl S-(l-butox -2-meth 1 r0 1 hosphorothlolothionate. y y) p py p (0H3)zOH-OH-O (CH-MOE:

SP (S) (OQzHs):

3. 0, O-Diethyl S-[l-(Mhloroethoxy) ethyl] phosphorothiolothionate.

CHs-OH-O-OHzOHaOl SP (S) (O C2H5) 2 4. O, O-Diethyl S-(l-methyl-Z-vinyloxy) ethyl phosphorothiolothiouate.

100 (no kill at 100 p.p.m.).

5 6 l'eoclalmi h h d h th m a omocHomomooI-n folhulfianop osp orus compoun s avmg e s ctur H H I M: I

R S 0R 5. As a composition of matter, O-ethyl, O-methyl S- \H (1,3,3-t-1imethoxypropyl)'phosphorothiolothionate having PS-(|3HCHz(3H the formula: R20 0B3 0R5 CHsO wherein R and R are selected from the group consisting of lower alkyl, lower haloalkyl and lower alkoxyalkyl and HS )SOH CHFCHwCHE) R R and R are alkyl radicals containing 1 to 2 carbon CIHBO atoms- 6. As a composition of matter, 0,0diethyl S-( l-meth As a composition of Qpoxy-3,3-diethoxypropy1) phosphorothiolothionate having tnmethoxypropyl) phosphorothiolothlonate having the the f r l formula: CH OOH--CHr-CH(OC2H5)I omoon-om-omocnm smsxooflmh SP(S)(OC2H5)2 3. As a composition of matter, 0,0-dimethyl S-(1,3,3 References Cited in the file of this patent trimethoxypropyl) phosphorothiolothionate having the UNITED STATES PATENTS f l a H CH H H O H 2 2,565,920 Hook a a1. Aug. 28, 1951 0 C 2,586,655 Hook et a1. Feb. 18, 1952 SP(S)(OCH;), 4. As a composition of matter, 0,0-bis(2,2,2-trichloro- FOREIGN PATENTS ethyl) S-(1,3,3-trimethoxypropy1) phosphorotholothionate 311,106 Switzerland Jan. 31, 1956 having the formula: 7 311,463 Switzerland J an. 31, 1956 

1. ORGANOPHOSPHORUS COMPOUNDS HAVING THE STRUCTURAL FORMULA: 